Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid-fluid molecular parameters for the system amorphous silica-Ar and amorphous silica-N₂, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.     

鸟嘌呤和次黄嘌呤的铜络合物的吸附作用和伏安特性研究

本文研究了鸟瞟呤(Gua)和次黄嘌呤(Hxa)铜络合物在悬汞电极(HMDE)上的吸附作用和电极反应机理,溶液中形成的1:1络合物有强烈吸附性,通过分子结构的比较,推断出Cu~(2+)与Gua和Hxa的咪唑环N(7)和外环氧O(6)原子结合形成封闭的五元环。嘌呤环的π-电子有使分子呈平面吸附的趋势,但是Gua络合物分子优先取“倾斜”定向;随着表面吸附浓度增加,Hxa络合物分子存在从“平面”向“垂直”的再定向作用。本文测定了单层吸附浓度、包含的电量和每个分子占据的面积。络合物吸附得到S形等温线,它与Frumkin吸附等温线接近。本文还列出有关吸附参数B、a、△G_A~O和θ~*的计算结果。     

Large-scale production of cellulose-binding domains. Adsorption studies using CBD-FITC conjugates

A method for the gram-scale production of cellulose-binding domains (CBD) through the proteolytic digestion of a commercial enzymatic preparation (Celluclast) was developed. The CBD obtained, isolated from Trichoderma reesei cellobiohydrolase I, is highly pure and heavily glycosylated. The purified peptide has a molecular weight of 8.43 kDa, comprising the binding module, a part of the linker, and about 30% glycosidic moiety. Its properties may thus be different from recombinant ones expressed in bacteria. CBD-fluorescein isothiocyanate conjugates were used to study the CBD-cellulose interaction. The presence of fluorescent peptides adsorbed on crystalline and amorphous cellulose fibers suggests that amorphous regions have a higher concentration of binding sites. The adsorption is reversible, but desorption is a very slow process.     

Influence of boric acid on the electrochemical deposition of Ni

The electrolytic deposition of Ni onto a paraffin-impregnated graphite electrode from supporting chloride electrolyte (0.5 mol dm⁻³ NaCl) adjusted to the required pH using dilute HCl is investigated. The effect of electrolyte composition on the Ni electrodeposition is studied using linear sweep voltammetry in the cathodic region. An elimination voltammetry procedure was applied to evaluate the polarization curves. The aim of this work was to deduce the mechanism of Ni reduction in the chloride bath as well as the influence of boric acid on this. Positively-charged NiCl⁺ ions were found to be the electroactive particles in the Ni reduction mechanism. The strong competition between the NiCl⁺, Cl⁻ and H⁺ ions for active sites at the electrode is discussed. Kinetically-controlled adsorption/desorption processes of various species were also confirmed using elimination voltammetry with a linear scan. The evolution of gaseous hydrogen, catalyzed by the freshly-deposited Ni, accompanies the electrodeposition process. The presence of boric acid at a sufficiently high concentration inhibits the deposition of Ni and, at the same time, improves the morphology and brightness, as well as the adhesion of the deposited Ni. Elimination voltammetry with a linear scan is an efficient way to evaluate current–potential curves that reflect the electrodeposition of one-component Ni coatings. By eliminating selected currents, additional interesting and useful information can be obtained from voltammetric data.     

Synergistic effect between 4-(2-pyridylazo) resorcin and chloride ion on the corrosion of cold rolled steel in 0.5 M sulfuric acid

The corrosion inhibition of 1-(2-pyridylazo)-2-naphthol (PAR) on the corrosion of cold rolled steel in 0.5 M sulfuric acid (H₂SO₄) was studied using weight loss method and potentiodynamic polarization method. Results obtained revealed that together with chloride ion, PAR is an effective corrosion inhibitor for steel corrosion in sulfuric acid. It was found that for steel corrosion inhibition in the presence of single PAR in sulfuric acid the Temkin adsorption isotherm may be used to explain the adsorption phenomenon. For the mixture of PAR and NaCl used as corrosion inhibitor, however, the Langmuir adsorption isotherm can be used to satisfactorily elucidate the adsorption of mixture of PAR and NaCl. Potentiodynamic polarization studies showed that single PAR mainly acts as a cathodic inhibitor for the corrosion of steel in 0.5 M sulfuric acid. The mixture of PAR and chloride ion, however, acts as a mixed type inhibitor that mainly inhibits cathodic reaction of the steel corrosion in sulfuric acid. By means of electrochemical polarization tests, a desorption potential at ca. −370 mV was observed for the adsorption of mixture of PAR and chloride ion, when potential reaches this value, adsorbed inhibitor molecule heavily departs from the steel surface. For the mixture of PAR and chloride ion, thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy were obtained from experimental data of the temperature studies of the inhibition process at four temperatures ranging from 30 to 45 °C, the kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, and the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The most suitable range of inhibitor concentration was discussed. The inhibitive action was satisfactorily explained by using both thermodynamic and kinetic models. Synergism between chloride ion and PAR was proposed. The results obtained from weight loss and potentiodynamic polarization were in good agreement.     

粒径和流速对吸附速率的影响

本文主要考察了吸附剂的粒径大小及动态循环时流速大小对吸附速率的影响，根据膜扩散限制和孔隙扩散限制的理论模型对其影响作了定量描述。     

A model of adsorption at liquid-solid interface involving association in the bulk phase

A model of monolayer adsorption of binary liquid mixtures on homogeneous and heterogeneous solid surfaces involving association of one component in the bulk phase is discussed. Suitable model calculations, illustrating association and heterogeneity effects, have been performed according to an equation derived for adsorption excess. This equation has been examined by using the experimental data of adsorption of alcohols from benzene andn-heptane on silica gel.

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Adsorptionsmodell für die Grenzfläche Feststoff-Flüssigkeit unter Berücksichtigung der Assoziation in der Flüssigkeitsphase

Zusammenfassung Es wird ein Adsorptionsmodell binärer, flüssiger Mischungen an homogenen und heterogenen Oberflächen von Feststoffen unter Beachtung der Assoziation eines der Bestandteile in der Flüssigkeitsphase diskutiert. Mit der aus dem Oberflächenüberschuß abgeleiteten Gleichung wurden entsprechende Modellberechnungen durchgeführt, die die mit Assoziation und Heterogenität verbundenen Effekte illustrieren. Die Gleichung wurde für die experimentellen Daten der Alkoholadsorption aus Benzol undn-Heptan an Kieselgel überprüft.

     

Human insulin and desamido human insulin isotherms in ethanol-water reversed phase systems

The multi-component isotherms for human insulin (HI) and desamido human insulin (dHI) over reversed phase packing (C18) and with 29.8% (w/w) ethanol-water as mobile phase have been determined experimentally. The isotherms of HI in ethanol-water differ from those obtained with the more commonly applied methanol-water and acetonitrile-water mobile phase, as described in this paper. The isotherm exhibits anti Langmuirian behavior and can be very well modeled by an anti Langmuir isotherm presented in this paper. The HI and dHI anti Langmuir isotherm are determined as: qHI = (8.4C(HI) + 3C(HI)CdHI)/(1 - 0.05C(HI) - 0.14CdHI + 0.04C(HI)CdHI) and qdHI = (11.4CdHI + 2C(HI)CdHI)/ (1 - 0.05C(HI) - 0.14CdHI + 0.04C(HI)CdHI)